Toward a Resolution of the Static Correlation Problem in Density Functional Theory from Semidefinite Programming

Kohn-Sham density functional theory (DFT) has long struggled with the accurate description of strongly correlated and open shell systems, and improvements have been minor even in the newest hybrid functionals. In this Letter we treat the static correlation in DFT when frontier orbitals are degenerate by the means of using a semidefinite programming (SDP) approach to minimize the system energy as a function of the N-representable, non-idempotent 1-electron reduced density matrix. While showing greatly improved singlet-triplet gaps for local density approximation and generalized gradient approximation (GGA) functionals, the SDP procedure reveals flaws in modern meta and hybrid GGA functionals, which show no major improvements when provided with an accurate electron density.

Automated summary

By using a semidefinite programming approach, improvements have been made in accurately describing strongly correlated and open shell systems in Kohn-Sham density functional theory, resulting in enhanced singlet-triplet gaps for local density approximation and generalized gradient approximation functionals. Additionally, flaws in modern meta and hybrid GGA functionals were revealed, showing no significant improvements even with accurate electron density provided.